Combined First-Principle Calculations and Experimental Study on Multi-Component Olivine Cathode for Lithium Rechargeable Batteries

被引：126

作者：

Gwon, Hyeokjo ^{[1
]}

Seo, Dong-Hwa ^{[1
]}

Kim, Sung-Wook ^{[1
]}

Kim, Jongsoon ^{[1
]}

Kang, Kisuk ^{[1
]}

机构：

[1] Korea Adv Inst Sci & Technol, Inst Ecoenergy, Taejon 305701, South Korea

来源：

ADVANCED FUNCTIONAL MATERIALS | 2009年 / 19卷 / 20期

关键词：

ELECTROCHEMICAL PERFORMANCE; ELECTRONIC-STRUCTURE; ROOM-TEMPERATURE; PHOSPHO-OLIVINES; PHASE-STABILITY; HIGH-POWER; LIFEPO4; TRANSFORMATIONS; DIFFRACTION; CAPACITY;

D O I：

10.1002/adfm.200900414

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The electrochemical properties and phase stability of the multi-component olivine compound LiMn1/3Fe1/3Co1/3PO4 are studied experimentally and with first-principles calculation. The formation of a solid solution between LiMnPO4, LiFePO4, and LiCoPO4 at this composition is confirmed by XRD patterns and the calculated energy. The experimental and first-principle results indicate that there are three distinct regions in the electrochemical profile at quasi-open-circuit circuit potentials of similar to 3.5V, similar to 4.1V, and similar to 4.7V, which are attributed 50 Fe3+/Fe-2+,Fe- , Mn3+/Mn2+, and Co3+/Co2+ redox couples, respectively. However, exceptionally large polarization is observed only for the region near 4.1V of Mn3+/Mn2+ redox couples, implying; an intrinsic charge transfer problem. An ex situ XRD study reveals that the reversible one-phase reaction of Li extraction/insertion mechanism prevails, unexpectedly, for all lithium compositions of LixMn1/3Fe1/3Co1/3PO4 (0 <= x <= 1) at room temperature. This is the first demonstration that the well-ordered non-nanocrystalline (less than 1% Li-M disorder and a few hundred nanometer size particle) olivine electrode can be operated solely in a one-phase mode.

引用

页码：3285 / 3292

页数：8

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